US20090306370A1 - Method Of Manufacturing An Organic Silicon Compound That Contains A Methacryloxy Group Or An Acryloxy Group - Google Patents

Method Of Manufacturing An Organic Silicon Compound That Contains A Methacryloxy Group Or An Acryloxy Group Download PDF

Info

Publication number
US20090306370A1
US20090306370A1 US12/064,208 US6420806A US2009306370A1 US 20090306370 A1 US20090306370 A1 US 20090306370A1 US 6420806 A US6420806 A US 6420806A US 2009306370 A1 US2009306370 A1 US 2009306370A1
Authority
US
United States
Prior art keywords
group
phenothiazine
carbon atoms
organic silicon
silicon compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US12/064,208
Other versions
US8148565B2 (en
Inventor
Keiji Wakita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Toray Co Ltd
Original Assignee
Dow Corning Toray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Co Ltd filed Critical Dow Corning Toray Co Ltd
Assigned to DOW CORNING TORAY COMPANY, LTD. reassignment DOW CORNING TORAY COMPANY, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WAKITA, KEIJI
Publication of US20090306370A1 publication Critical patent/US20090306370A1/en
Application granted granted Critical
Publication of US8148565B2 publication Critical patent/US8148565B2/en
Assigned to DOW TORAY CO., LTD. reassignment DOW TORAY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DOW CORNING TORAY CO., LTD.
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D279/00Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/101,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/141,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18[b, e]-condensed with two six-membered rings
    • C07D279/20[b, e]-condensed with two six-membered rings with hydrogen atoms directly attached to the ring nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/0834Compounds having one or more O-Si linkage
    • C07F7/0838Compounds with one or more Si-O-Si sequences
    • C07F7/0872Preparation and treatment thereof
    • C07F7/0876Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878Si-C bond
    • C07F7/0879Hydrosilylation reactions
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • C07F7/1872Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/38Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents

Definitions

  • the present invention relates to a novel method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group and that is widely used as a silane coupling agent and a polymerizable monomer.
  • organic silicon compounds that contain methacryloxy groups or acryloxy groups are subject to spontaneous polymerization, and selection of polymerization inhibitors for preventing the undesired spontaneous polymerization is a matter of great importance.
  • Japanese Unexamined Patent Application Publication [hereinafter referred to as Kokai] S62-283983 (equivalent to EP 0247501) discloses a manufacturing method where an aromatic sulfur compound represented by phenothiazine is used as an inhibitor during distillation and synthesis of an organic silane that contains methacryloxy and acryloxy groups.
  • an aromatic sulfur compound represented by phenothiazine is used as an inhibitor during distillation and synthesis of an organic silane that contains methacryloxy and acryloxy groups.
  • the phenothiazine is easily mixed with fractions, and since the final product is admixed with phenothiazine, it is subject to severe coloration.
  • Kokai H5-186478 discloses inhibition of polymerization of an acryloxysilane and methacryloxy silane by adding to the composition an N,N-dialkylaminomethylene phenol.
  • Kokai H5-230143 discloses a polymerization inhibitor having an active ingredient in the form of an isocyanuric acid hydroxybenzyl ester derivative, e.g., isocyanuric acid tris(3,5-di-tert-butyl-4-hydroxybenzyl)ester.
  • Kokai H7-25907 discloses a polymerization inhibitor having an active ingredient in the form of a 2,6-di-t-butyl-4-hydroxymethylphenol.
  • the inventors herein have found that a high-quality organic silicon compound that contains a methacryloxy group or an acryloxy group can be produced without risk of coloration and without spontaneous polymerization, even under vigorous production conditions, if the manufacturing process is carried out with the use of a phenothiazine derivative having a molecular weight no less than 240. Thus the inventors arrived at the present invention.
  • the method of the invention for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group consists of manufacturing or conducting purification by distillation the product either in the presence of a phenothiazine derivative having a molecular weight above at least 240.
  • the aforementioned phenothiazine derivative is a compound selected from the group consisting of the following: a phenothiazine substituted with alkyl having four or more carbon atoms, dibenzophenothiazine, phenothiazine substituted with acyl having 2 to 18 carbon atoms, N,N′ phenothiazine dimer, a compound represented by formula (1) given below:
  • R 1 is an aralkyl group having 7 to 18 carbon atoms
  • R 2 is selected from a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms
  • m and n are integers from 0 to 2, and where the following condition is satisfied: m+n ⁇ 1
  • R 2 is the same as defined above, R 3 is either a hydrogen atom or is selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; R 4 is either a hydrogen atom or is selected from an alkyl group having 1 to 18 carbon atoms or an acyl group having 2 to 18 carbon atoms; X is a group selected from a methylene group, ⁇ -methylmethylene group, and ⁇ -phenylmethylene group; and “r” is a number represented by an average value between 1 and 5.
  • phenothiazine derivatives of the aforementioned type are compounds selected from the group consisting of 3-( ⁇ -methylbenzyl)phenothiazine, 1-( ⁇ -methylbenzyl)phenothiazine, 3.7-bis( ⁇ -methylbenzyl)phenothiazine, 3-( ⁇ , ⁇ -dimethylbenzyl)phenothiazine, 3,7-( ⁇ , ⁇ -dimethylbenzyl)phenothiazine, 10-acetylphenothiazine, and 3,3′-methylene-bis(phenothiazine).
  • the aforementioned organic silicon compound that contains a methacryloxy group or an acryloxy group can be represented by the following formula (3):
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a bivalent organic group
  • R 7 is an alkyl group
  • R 8 is either a halogen atom or is selected from an alkoxy group or an alkyloxyalkoxy group
  • “p” is an integer from 1 to 3.
  • Most preferable is the organic silicon compound of the aforementioned type, wherein R 8 in formula (3) is a bromine atom or a chlorine atom.
  • a stable composition that contains the aforementioned methacryloxy- or acryloxy-containing organic silicon compound can be prepared by combining the aforementioned organic silicon compound with a phenothiazine derivative that has a molecular weight of 240 or greater and that is used in an amount sufficient for stabilizing the compound, and by subjecting the organic silicon compound to purification by distillation prior to use.
  • the method of the invention inhibits spontaneous polymerization under severe production conditions of high temperature and strong acidity inherent in an industrial manufacturing process and since purification by distillation completely removes the polymerization inhibitor which constitutes a source of coloration of the target product, it becomes possible to efficiently produce a high-quality, coloration-resistant organic silicon compound that contains a methacryloxy group or an acryloxy group.
  • Phenothiazine derivatives suitable for the purposes of the present invention may be comprised of known phenothiazine derivatives having molecular weights equal to or greater than 240, preferably greater than 300, and even more preferably, greater than 400.
  • Such phenothiazine derivatives may be exemplified by the following compounds: 3-t-butyl-phenothiazine, 3-t-amylphenothiazine, 10-t-butyl-phenothiazine, 3-(1,1,3,3-tetramethylbutyl)phenothiazine, or similar phenothiazines substituted with alkyls having four or more carbon atoms; 1,2-benzophenothiazine, or similar benzophenothiazines; 1,2,6,7-benzophenothiazine, or similar benzophenothiazine; 1-acetylphenothiazine, 10-acetylphenothiazine, or similar diphenothiazines substituted with acyls having 2 to 18 carbon atoms; 10,10′-diphenothiazine, 1,1′-dimethyl-10,10′-diphenothiazine, 2,2′,6,6′-tetramethyl-10,10′
  • R 1 designates benzyl groups, ⁇ -methylbenzyl groups, ⁇ , ⁇ -dimethylbenzyl groups, or similar aralkyl groups having 7 to 18 carbon atoms or 7 to 12 carbon atoms, ⁇ -methylbenzyl groups and ⁇ , ⁇ -dimethylbenzyl groups being preferable; groups designated by R 1 may be the same or different.
  • R 2 designates hydrogen atoms or groups selected from linear-chain or branch-chain alkyl groups having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, acetyl groups and aralkyl groups having 7 to 18 carbon atoms, preferably, 7 to 12 carbon atoms, and benzoyl groups or similar acyl groups having 2 to 18 carbon atoms, preferably, 2 to 7 carbon atoms.
  • Most preferable are hydrogen atoms or acetyl groups, especially, hydrogen atoms.
  • R 3 designates hydrogen atoms or groups selected from linear-chain or branch-chain alkyl groups having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, acetyl groups and aralkyl groups having 7 to 18 carbon atoms, preferably, 7 to 12 carbon atoms, and benzoyl groups or similar acyl groups having 2 to 18 carbon atoms, preferably, 2 to 7 carbon atoms.
  • Preferable are hydrogen atoms, aralkyl groups having 7 to 12 carbon atoms, but most preferable are hydrogen atoms, benzyl groups, ⁇ -methylbenzyl groups, ⁇ , ⁇ -dimethylbenzyl groups, and especially, hydrogen atoms.
  • R 4 designates hydrogen atoms or groups selected from linear-chain or branch-chain alkyl groups and acetyl groups having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, and benzoyl groups or similar acyl groups having 2 to 18 carbon atoms, preferably, 2 to 7 carbon atoms. Preferable are hydrogen atoms or acetyl groups.
  • X designates a group selected from a methylene group, ⁇ -methylmethylene group, and ⁇ -phenylmethylene group; “m” and “n” are integers from 0 to 2 that satisfy the following condition: “(m+n) ⁇ 1; “r” is a number represented by an average value of 1 to 5 and that preferably is in the range of 1 to 2, and even more preferably, in the range of 1 to 1.5.
  • preferable compound of formula (1) 3-( ⁇ -methylbenzyl)phenothiazine, 1-( ⁇ -methylbenzyl)phenothiazine, 3,7-bis( ⁇ -methylbenzyl)phenothiazine, 3-( ⁇ , ⁇ -dimethylbenzyl)phenothiazine, and 3,7-bis( ⁇ , ⁇ -dimethylbenzyl)phenothiazine.
  • the aforementioned phenothiazine derivatives even in small quantities, produce a sufficient effect on organic silicon compounds that contain methacryloxy or acryloxy groups.
  • the best results are obtained when, in terms of a weight ratio, the phenothiazine derivative is mixed with the aforementioned organosilicon compound in an amount of 10 to 5000 ppm, preferably 100 to 2000 ppm.
  • phenothiazine derivatives are suitable for use in the manufacture of an organic silicon compound of below-given formula (3) that contains a methacryloxy group or an acryloxy group:
  • R 5 is a hydrogen atom or a methyl group
  • R 6 is a bivalent organic group, preferable of which are methylene, ethylene, propylene, butylenes, isobutylene, or similar alkylene groups
  • R 7 is an alkyl group, preferably, methyl group
  • R 8 is either a chlorine atom, bromine atom or a similar halogen atom or is selected from a methoxy group, ethoxy group, or a similar alkoxy group, or a methoxyethoxy group, ethoxymethoxy group, or a similar alkyloxyalkoxy group.
  • “p” is an integer from 1 to 3.
  • the following are specific examples of the aforementioned organic silicon compounds: methacryloxymethyl trimethoxysilane, methacryloxypropyl trimethoxysilane, acryloxypropyl trimethoxysilane, methacryloxypropyl methyldimethoxysilane, methacryloxypropyl triethoxysilane, acryloxypropyl triethoxysilane, methacryloxypropyl trichlorosilane, methacryloxypropyl methyldichlorosilane, methacryloxypropyl dimethylchlorosilane, methacryloxyisobutyl trimethoxysilane, and methacryloxyisobutyl trichlorosilane.
  • Methacryloxy- and acryloxy-containing organic silicon compounds may be exemplified by bis(methacryloxypropyl) tetramethyldisiloxane, methacryloxypropyl tris(trimethylsiloxy)siloxane, acryloxytrimethylsilane, methacryloxytrimethylsilane, methacryloxyphenyldimethylsilane, or the like.
  • the aforementioned phenothiazine derivatives can also efficiently inhibit spontaneous polymerization in organic silicon compounds of formula (3) that have methacryloxy or acryloxy groups where R 8 in the above formula is a halogen atom. Since such a methacryloxy- or acryloxy-containing organic silicon compounds are strongly acidic and therefore are more readily subject to spontaneous polymerization, they have to be handled with caution.
  • the aforementioned phenothiazine derivatives can be easily and completely removed from a crude methacryloxy- or acryloxy-containing organic silicon compounds by distillation.
  • the distillation operation can be carried out without the use of a distillation column, with the use of a distillation column, by distillation in vacuum, by thin-film distillation, or by any other known method of distillation. Any of the above distillation methods protects the methacryloxy- or acryloxy-containing organic silicon compounds from mixing with phenothiazine derivatives, and thus prevents coloration of the target product. Furthermore, since the entire phenothiazine derivative remains in the reactor, polymerization is efficiently prevented also in the reactor that may create a problem during distillation.
  • the aforementioned phenothiazine derivative alone demonstrates sufficient polymerization inhibiting capacity, but, if necessary, it can be additionally combined with known polymerization inhibitors, such as hindered-phenol or amine-type polymerization inhibitors.
  • known polymerization inhibitors such as hindered-phenol or amine-type polymerization inhibitors.
  • a methacryloxypropyl trichlorosilane was synthesized by a known method where allyl methacrylate and trichlorosilane were used as starting materials.
  • 20 g of the obtained product and 5 mg of a styrenated phenothiazine (ANTAGE STDP-N, molecular weight was 407.6; the product of Kawaguchi Chemical Company, Ltd.) was sealed in a bottle with a threaded cap and heated in a 150° C. oil bath.
  • the obtained product was not gelled and maintained flowability even 20 hours after the above-described treatment.
  • the product was obtained by the same method as in Practical Example 1, except that 5 mg of a 10-acetylphenothiazine of below-given formula (5) were used instead of the styrenated phenothiazine of formula (4).
  • the obtained product was not gelled and maintained flowability even 20 hours after the above-described treatment.
  • the 10-acetylphenothiazine of formula (5) was synthesized by the following method.
  • a 200-ml four-neck flask was loaded with 19.93 g (0.1 mole) of phenothiazine, 15.31 g (0.15 mole) of acetic anhydride, and 40 g of xylene, and the contents were subjected to heating under reflux conditions for 6 hours.
  • the reaction liquid was cooled, the precipitate was separated by filtering, and the product washed with methanol.
  • 22.6 g of 10-acetylphenothiazine having a molecular weight of 241.3 were obtained.
  • the product was obtained by the same method as in Practical Example 1, except that 2.5 mg of a phenothiazine derivative of below-given formula (6) were used instead of the styrenated phenothiazine of formula (4).
  • the obtained product was not gelled and maintained flowability even 20 hours after the above-described treatment.
  • the phenothiazine derivative of formula (6) was synthesized by the following method.
  • a 200-ml four-neck flask was loaded with 4.98 g (0.25 mole) of phenothiazine and 18 g of tetrahydrofuran, and then a mixture composed of 6.0 g of a concentrated hydrochloric acid, 4.36 g of formalin, and 24 g of methanol was added dropwise at room temperature. The precipitate was separated by filtering, and the product was washed with methanol. As a result, 3.11 g of phenothiazine oligomer were obtained.
  • the products were obtained by the same method as in Practical Example 1, except that known polymerization inhibitors of the type shown in Table 1 were used instead of the styrenated phenothiazine. Within 10 hours after the preparation, the products were gelled and lost flowability.
  • a four-neck flask equipped with a stirrer was loaded with 867 g (6.87 mole) of allyl methacrylate, 0.2 g of a platinum-divinyltetramethylsiloxane complex (0.4 mmole of metallic platinum), and 2.7 g of a styrenated phenothiazine (ANTAGE STDP-N, molecular weight was 407.6; the product of Kawaguchi Chemical Company, Ltd.).
  • the content was heated at 80° C., and 912 g (6.73 mole) of trichlorosilane were added dropwise. Following this, 647 g (20.2 mole) of methanol were added dropwise, and the product was neutralized by blowing ammonia into the product.
  • the precipitate was separated by filtering, the product was distilled under a reduced pressure of 7 mmHg, and a 115 to 122° C. fraction was taken.
  • the obtained fraction comprised 1229 g of a methacryloxypropyl trimethoxysilane which was obtained with the yield of 74%.
  • the obtained product was exposed to direct sun rays, but no changes in color were observed.
  • the product was obtained by the same method as in Practical Example 4, except that 1.6 g (6.6 mmole) of a 10-acetylphenothiazine of formula (5) were used instead of the styrenated phenothiazine of formula (4).
  • the obtained fraction comprised 1203 g of a methacryloxypropyl trimethoxysilane which was obtained with the yield of 72%. For two days the obtained product was exposed to direct sun rays, but no changes in color were observed.
  • the product was obtained by the same method as in Practical Example 4, except that 1.4 g of a phenothiazine derivative of formula (6) were used instead of the styrenated phenothiazine of formula (4).
  • the obtained fraction comprised 1171 g of a methacryloxypropyl trimethoxysilane which was obtained with the yield of 70%. For two days the obtained product was exposed to direct sun rays, but no changes in color were observed.
  • the product was obtained by the same method as in Practical Example 4, except that phenothiazine was used instead of the styrenated phenothiazine of formula (4). For two days the obtained product was exposed to direct sun rays, and the color was changed to brown.
  • the product was obtained by the same method as in Practical Example 4, except that 2,6-di-t-butyl-4-methylphenol was used instead of the styrenated phenothiazine of formula (4).
  • a polymer was formed in the reactor in the final stage of distillation, and further distillation could not be continued.

Abstract

A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, the method being characterized by the fact that manufacturing or conducting purification by distillation is carried out in the presence of a phenothiazine derivative having a molecular weight equal to or higher than 240. And a stable composition comprising an organic silicon compound that contains a methacryloxy group or an acryloxy group and a phenothiazine derivative having a molecular weight equal to or higher than 240 and used in an amount sufficient to stabilize the aforementioned organic silicon compound.

Description

    TECHNICAL FIELD
  • The present invention relates to a novel method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group and that is widely used as a silane coupling agent and a polymerizable monomer.
  • BACKGROUND ART
  • Since under the effect of heat that is generated either during industrial-scale synthesis or during purification by distillation, organic silicon compounds that contain methacryloxy groups or acryloxy groups are subject to spontaneous polymerization, and selection of polymerization inhibitors for preventing the undesired spontaneous polymerization is a matter of great importance.
  • Japanese Unexamined Patent Application Publication [hereinafter referred to as Kokai] S62-283983 (equivalent to EP 0247501) discloses a manufacturing method where an aromatic sulfur compound represented by phenothiazine is used as an inhibitor during distillation and synthesis of an organic silane that contains methacryloxy and acryloxy groups. However, during purification by distillation, the phenothiazine is easily mixed with fractions, and since the final product is admixed with phenothiazine, it is subject to severe coloration.
  • Kokai H5-186478 (equivalent to EP 0520477) discloses inhibition of polymerization of an acryloxysilane and methacryloxy silane by adding to the composition an N,N-dialkylaminomethylene phenol. Kokai H5-230143 discloses a polymerization inhibitor having an active ingredient in the form of an isocyanuric acid hydroxybenzyl ester derivative, e.g., isocyanuric acid tris(3,5-di-tert-butyl-4-hydroxybenzyl)ester. Kokai H7-25907 discloses a polymerization inhibitor having an active ingredient in the form of a 2,6-di-t-butyl-4-hydroxymethylphenol. Although the last-mentioned polymerization inhibitors are relatively resistant to coloration when mixed with the final product, they are still unsuitable for production under conditions of high temperature and strong acidity inherent in an industrial manufacturing process.
  • DISCLOSURE OF INVENTION
  • It is an object of the present invention to provide an efficient method for manufacturing a high-quality, coloration-resistant organic silicon compound that contains a methacryloxy group or an acryloxy group and inhibits spontaneous polymerization under conditions of high temperature and strong acidity inherent in an industrial manufacturing process.
  • The inventors herein have found that a high-quality organic silicon compound that contains a methacryloxy group or an acryloxy group can be produced without risk of coloration and without spontaneous polymerization, even under vigorous production conditions, if the manufacturing process is carried out with the use of a phenothiazine derivative having a molecular weight no less than 240. Thus the inventors arrived at the present invention.
  • More specifically, the method of the invention for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group consists of manufacturing or conducting purification by distillation the product either in the presence of a phenothiazine derivative having a molecular weight above at least 240.
  • The aforementioned phenothiazine derivative is a compound selected from the group consisting of the following: a phenothiazine substituted with alkyl having four or more carbon atoms, dibenzophenothiazine, phenothiazine substituted with acyl having 2 to 18 carbon atoms, N,N′ phenothiazine dimer, a compound represented by formula (1) given below:
  • Figure US20090306370A1-20091210-C00001
  • (where R1 is an aralkyl group having 7 to 18 carbon atoms, and R2 is selected from a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; “m” and “n” are integers from 0 to 2, and where the following condition is satisfied: m+n≧1), and a compound of the following formula (2):
  • Figure US20090306370A1-20091210-C00002
  • (where R2 is the same as defined above, R3 is either a hydrogen atom or is selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; R4 is either a hydrogen atom or is selected from an alkyl group having 1 to 18 carbon atoms or an acyl group having 2 to 18 carbon atoms; X is a group selected from a methylene group, α-methylmethylene group, and α-phenylmethylene group; and “r” is a number represented by an average value between 1 and 5. Preferable phenothiazine derivatives of the aforementioned type are compounds selected from the group consisting of 3-(α-methylbenzyl)phenothiazine, 1-(α-methylbenzyl)phenothiazine, 3.7-bis(α-methylbenzyl)phenothiazine, 3-(α,α-dimethylbenzyl)phenothiazine, 3,7-(α,α-dimethylbenzyl)phenothiazine, 10-acetylphenothiazine, and 3,3′-methylene-bis(phenothiazine).
  • The aforementioned organic silicon compound that contains a methacryloxy group or an acryloxy group can be represented by the following formula (3):

  • CH2═C(R5)COO—R6—Si(R7)3-p(R8)p  (3)
  • (where R5 is a hydrogen atom or a methyl group, R6 is a bivalent organic group, R7 is an alkyl group, and R8 is either a halogen atom or is selected from an alkoxy group or an alkyloxyalkoxy group; and “p” is an integer from 1 to 3). Most preferable is the organic silicon compound of the aforementioned type, wherein R8 in formula (3) is a bromine atom or a chlorine atom.
  • Furthermore, a stable composition that contains the aforementioned methacryloxy- or acryloxy-containing organic silicon compound can be prepared by combining the aforementioned organic silicon compound with a phenothiazine derivative that has a molecular weight of 240 or greater and that is used in an amount sufficient for stabilizing the compound, and by subjecting the organic silicon compound to purification by distillation prior to use.
  • Since the method of the invention inhibits spontaneous polymerization under severe production conditions of high temperature and strong acidity inherent in an industrial manufacturing process and since purification by distillation completely removes the polymerization inhibitor which constitutes a source of coloration of the target product, it becomes possible to efficiently produce a high-quality, coloration-resistant organic silicon compound that contains a methacryloxy group or an acryloxy group.
  • BEST MODE FOR CARRYING OUT THE INVENTION
  • Phenothiazine derivatives suitable for the purposes of the present invention may be comprised of known phenothiazine derivatives having molecular weights equal to or greater than 240, preferably greater than 300, and even more preferably, greater than 400.
  • Such phenothiazine derivatives may be exemplified by the following compounds: 3-t-butyl-phenothiazine, 3-t-amylphenothiazine, 10-t-butyl-phenothiazine, 3-(1,1,3,3-tetramethylbutyl)phenothiazine, or similar phenothiazines substituted with alkyls having four or more carbon atoms; 1,2-benzophenothiazine, or similar benzophenothiazines; 1,2,6,7-benzophenothiazine, or similar benzophenothiazine; 1-acetylphenothiazine, 10-acetylphenothiazine, or similar diphenothiazines substituted with acyls having 2 to 18 carbon atoms; 10,10′-diphenothiazine, 1,1′-dimethyl-10,10′-diphenothiazine, 2,2′,6,6′-tetramethyl-10,10′-diphenothiazine, or similar N,N′-phenothiazine dimmers; a compound of following formula (1):
  • Figure US20090306370A1-20091210-C00003
  • and a compound of following formula (2):
  • Figure US20090306370A1-20091210-C00004
  • Most preferable from the viewpoint of availability is the compound of formula (1).
  • In the above formulae, R1 designates benzyl groups, α-methylbenzyl groups, α,α-dimethylbenzyl groups, or similar aralkyl groups having 7 to 18 carbon atoms or 7 to 12 carbon atoms, α-methylbenzyl groups and α,α-dimethylbenzyl groups being preferable; groups designated by R1 may be the same or different.
  • R2 designates hydrogen atoms or groups selected from linear-chain or branch-chain alkyl groups having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, acetyl groups and aralkyl groups having 7 to 18 carbon atoms, preferably, 7 to 12 carbon atoms, and benzoyl groups or similar acyl groups having 2 to 18 carbon atoms, preferably, 2 to 7 carbon atoms. Most preferable are hydrogen atoms or acetyl groups, especially, hydrogen atoms.
  • R3 designates hydrogen atoms or groups selected from linear-chain or branch-chain alkyl groups having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, acetyl groups and aralkyl groups having 7 to 18 carbon atoms, preferably, 7 to 12 carbon atoms, and benzoyl groups or similar acyl groups having 2 to 18 carbon atoms, preferably, 2 to 7 carbon atoms. Preferable are hydrogen atoms, aralkyl groups having 7 to 12 carbon atoms, but most preferable are hydrogen atoms, benzyl groups, α-methylbenzyl groups, α,α-dimethylbenzyl groups, and especially, hydrogen atoms.
  • R4 designates hydrogen atoms or groups selected from linear-chain or branch-chain alkyl groups and acetyl groups having 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, and benzoyl groups or similar acyl groups having 2 to 18 carbon atoms, preferably, 2 to 7 carbon atoms. Preferable are hydrogen atoms or acetyl groups.
  • X designates a group selected from a methylene group, α-methylmethylene group, and α-phenylmethylene group; “m” and “n” are integers from 0 to 2 that satisfy the following condition: “(m+n)≧1; “r” is a number represented by an average value of 1 to 5 and that preferably is in the range of 1 to 2, and even more preferably, in the range of 1 to 1.5.
  • The following are specific examples of preferable compound of formula (1): 3-(α-methylbenzyl)phenothiazine, 1-(α-methylbenzyl)phenothiazine, 3,7-bis(α-methylbenzyl)phenothiazine, 3-(α,α-dimethylbenzyl)phenothiazine, and 3,7-bis(α,α-dimethylbenzyl)phenothiazine.
  • Compounds of formula (2) may be exemplified by compounds of the formulae given below, where “r” is the same as defined above:
  • Figure US20090306370A1-20091210-C00005
  • The aforementioned phenothiazine derivatives, even in small quantities, produce a sufficient effect on organic silicon compounds that contain methacryloxy or acryloxy groups. The best results are obtained when, in terms of a weight ratio, the phenothiazine derivative is mixed with the aforementioned organosilicon compound in an amount of 10 to 5000 ppm, preferably 100 to 2000 ppm.
  • The aforementioned phenothiazine derivatives are suitable for use in the manufacture of an organic silicon compound of below-given formula (3) that contains a methacryloxy group or an acryloxy group:

  • CH2═C(R5)COO—R6—Si(R7)3-p(R8)p  (3),
  • where R5 is a hydrogen atom or a methyl group, and R6 is a bivalent organic group, preferable of which are methylene, ethylene, propylene, butylenes, isobutylene, or similar alkylene groups; R7 is an alkyl group, preferably, methyl group; and R8 is either a chlorine atom, bromine atom or a similar halogen atom or is selected from a methoxy group, ethoxy group, or a similar alkoxy group, or a methoxyethoxy group, ethoxymethoxy group, or a similar alkyloxyalkoxy group. Most preferable are methoxy groups, ethoxy groups, chlorine atoms, or bromine atoms, especially, chlorine atoms or bromine atoms. In the above formula, “p” is an integer from 1 to 3. The following are specific examples of the aforementioned organic silicon compounds: methacryloxymethyl trimethoxysilane, methacryloxypropyl trimethoxysilane, acryloxypropyl trimethoxysilane, methacryloxypropyl methyldimethoxysilane, methacryloxypropyl triethoxysilane, acryloxypropyl triethoxysilane, methacryloxypropyl trichlorosilane, methacryloxypropyl methyldichlorosilane, methacryloxypropyl dimethylchlorosilane, methacryloxyisobutyl trimethoxysilane, and methacryloxyisobutyl trichlorosilane.
  • Methacryloxy- and acryloxy-containing organic silicon compounds, other than those mentioned above, may be exemplified by bis(methacryloxypropyl) tetramethyldisiloxane, methacryloxypropyl tris(trimethylsiloxy)siloxane, acryloxytrimethylsilane, methacryloxytrimethylsilane, methacryloxyphenyldimethylsilane, or the like.
  • The aforementioned phenothiazine derivatives can also efficiently inhibit spontaneous polymerization in organic silicon compounds of formula (3) that have methacryloxy or acryloxy groups where R8 in the above formula is a halogen atom. Since such a methacryloxy- or acryloxy-containing organic silicon compounds are strongly acidic and therefore are more readily subject to spontaneous polymerization, they have to be handled with caution.
  • The aforementioned phenothiazine derivatives can be easily and completely removed from a crude methacryloxy- or acryloxy-containing organic silicon compounds by distillation. The distillation operation can be carried out without the use of a distillation column, with the use of a distillation column, by distillation in vacuum, by thin-film distillation, or by any other known method of distillation. Any of the above distillation methods protects the methacryloxy- or acryloxy-containing organic silicon compounds from mixing with phenothiazine derivatives, and thus prevents coloration of the target product. Furthermore, since the entire phenothiazine derivative remains in the reactor, polymerization is efficiently prevented also in the reactor that may create a problem during distillation.
  • The aforementioned phenothiazine derivative alone demonstrates sufficient polymerization inhibiting capacity, but, if necessary, it can be additionally combined with known polymerization inhibitors, such as hindered-phenol or amine-type polymerization inhibitors. In the case of distillation, in particular, in order to inhibit polymerization of a gaseous phase, it is recommended to combine the phenothiazine derivative of the invention with p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, or similar polymerization inhibitors that have boiling points under atmospheric pressure below 300° C.
  • EXAMPLES
  • The invention will be further described more specifically with reference to the Practical Examples which are given below. It is understood that these examples should not construed as limiting the scope of the invention.
  • Practical Example 1
  • A methacryloxypropyl trichlorosilane was synthesized by a known method where allyl methacrylate and trichlorosilane were used as starting materials. 20 g of the obtained product and 5 mg of a styrenated phenothiazine (ANTAGE STDP-N, molecular weight was 407.6; the product of Kawaguchi Chemical Company, Ltd.) was sealed in a bottle with a threaded cap and heated in a 150° C. oil bath. The obtained product was not gelled and maintained flowability even 20 hours after the above-described treatment.
  • Figure US20090306370A1-20091210-C00006
  • Practical Example 2
  • The product was obtained by the same method as in Practical Example 1, except that 5 mg of a 10-acetylphenothiazine of below-given formula (5) were used instead of the styrenated phenothiazine of formula (4). The obtained product was not gelled and maintained flowability even 20 hours after the above-described treatment.
  • Figure US20090306370A1-20091210-C00007
  • The 10-acetylphenothiazine of formula (5) was synthesized by the following method. A 200-ml four-neck flask was loaded with 19.93 g (0.1 mole) of phenothiazine, 15.31 g (0.15 mole) of acetic anhydride, and 40 g of xylene, and the contents were subjected to heating under reflux conditions for 6 hours. The reaction liquid was cooled, the precipitate was separated by filtering, and the product washed with methanol. As a result, 22.6 g of 10-acetylphenothiazine having a molecular weight of 241.3 were obtained.
  • Practical Example 3
  • The product was obtained by the same method as in Practical Example 1, except that 2.5 mg of a phenothiazine derivative of below-given formula (6) were used instead of the styrenated phenothiazine of formula (4). The obtained product was not gelled and maintained flowability even 20 hours after the above-described treatment.
  • Figure US20090306370A1-20091210-C00008
  • The phenothiazine derivative of formula (6) was synthesized by the following method. A 200-ml four-neck flask was loaded with 4.98 g (0.25 mole) of phenothiazine and 18 g of tetrahydrofuran, and then a mixture composed of 6.0 g of a concentrated hydrochloric acid, 4.36 g of formalin, and 24 g of methanol was added dropwise at room temperature. The precipitate was separated by filtering, and the product was washed with methanol. As a result, 3.11 g of phenothiazine oligomer were obtained.
  • NMR analysis and gel-permeation chromatography (GPC) confirmed that the product had the structure of formula (6) where “r” was on average about 1.2 and molecular weight was on average about 453.
  • Comparative Examples 1 to 10
  • The products were obtained by the same method as in Practical Example 1, except that known polymerization inhibitors of the type shown in Table 1 were used instead of the styrenated phenothiazine. Within 10 hours after the preparation, the products were gelled and lost flowability.
  • Practical Example 4
  • A four-neck flask equipped with a stirrer was loaded with 867 g (6.87 mole) of allyl methacrylate, 0.2 g of a platinum-divinyltetramethylsiloxane complex (0.4 mmole of metallic platinum), and 2.7 g of a styrenated phenothiazine (ANTAGE STDP-N, molecular weight was 407.6; the product of Kawaguchi Chemical Company, Ltd.). The content was heated at 80° C., and 912 g (6.73 mole) of trichlorosilane were added dropwise. Following this, 647 g (20.2 mole) of methanol were added dropwise, and the product was neutralized by blowing ammonia into the product. The precipitate was separated by filtering, the product was distilled under a reduced pressure of 7 mmHg, and a 115 to 122° C. fraction was taken. The obtained fraction comprised 1229 g of a methacryloxypropyl trimethoxysilane which was obtained with the yield of 74%. For two days the obtained product was exposed to direct sun rays, but no changes in color were observed.
  • Practical Example 5
  • The product was obtained by the same method as in Practical Example 4, except that 1.6 g (6.6 mmole) of a 10-acetylphenothiazine of formula (5) were used instead of the styrenated phenothiazine of formula (4). The obtained fraction comprised 1203 g of a methacryloxypropyl trimethoxysilane which was obtained with the yield of 72%. For two days the obtained product was exposed to direct sun rays, but no changes in color were observed.
  • Practical Example 6
  • The product was obtained by the same method as in Practical Example 4, except that 1.4 g of a phenothiazine derivative of formula (6) were used instead of the styrenated phenothiazine of formula (4). The obtained fraction comprised 1171 g of a methacryloxypropyl trimethoxysilane which was obtained with the yield of 70%. For two days the obtained product was exposed to direct sun rays, but no changes in color were observed.
  • Comparative Example 11
  • The product was obtained by the same method as in Practical Example 4, except that phenothiazine was used instead of the styrenated phenothiazine of formula (4). For two days the obtained product was exposed to direct sun rays, and the color was changed to brown.
  • Comparative Example 12
  • The product was obtained by the same method as in Practical Example 4, except that 2,6-di-t-butyl-4-methylphenol was used instead of the styrenated phenothiazine of formula (4). A polymer was formed in the reactor in the final stage of distillation, and further distillation could not be continued.
  • TABLE 1
    Examples Polymerization Inhibitors Time to Gelling
    Appl. Ex. 1 Styrenated phenothiazine No gelling after 20 hr.
    Appl. Ex. 2 10-Acetylphenathiazene No gelling after 20 hr.
    Appl. Ex. 3 3,3′-Methylene bis (phenothiazine) No gelling after 20 hr.
    Comp. Ex. 1 p-methoxyphenol Gelling within 1 hr.
    Comp. Ex. 2 Hydroquinone Gelling within 1 hr.
    Comp. Ex. 3 t-butylpyrocatecol Gelling within 1 hr.
    Comp. Ex. 4 2,6-di-t-butyl-4-methylphenol Gelling after 3 hr.
    Comp. Ex. 5 2,6-di-t-butyl-4-dimethylaminomethylphenol Gelling after 8 hr.
    Comp. Ex. 6 4,4′-thio-bis (6-t-butyl-3-methylphenol) Gelling within 1 hr.
    Comp. Ex. 7 N-nitroso-phenylhydroxylamine hydrochloride salt Gelling within 1 hr.
    Comp. Ex. 8 2,4-bis (n-octylthio)-6-(4-hydroxy-3,5-di-t- Gelling after 4 hr.
    butylanilino)-1,3,5-triazine
    Comp. Ex. 9 Pentaerythritol tetrakis [3-(3,5-di-t-butyl-4- Gelling within 1 hr.
    hydroxyphenyl) propionate
    Comp. Ex. 10 l,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4- Gelling within 1 hr.
    hydroxybenzyl) benzene

Claims (10)

1. A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, the method being characterized by the fact that manufacturing or conducting purification by distillation is carried out in the presence of a phenothiazine derivative having a molecular weight equal to or higher than 240.
2. The method of claim 1 for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, wherein said phenothiazine derivative is a compound selected from the following: a phenothiazine substituted with alkyl having four or more carbon atoms, dibenzophenothiazine, phenothiazine substituted with acyl having 2 to 18 carbon atoms, an N,N′ phenothiazine dimer, a compound represented by formula (1) given below:
Figure US20090306370A1-20091210-C00009
(where R1 is an aralkyl group having 7 to 18 carbon atoms, and R2 is selected from a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; “m” and “n” are integers from 0 to 2, and where the following condition is satisfied: m+n≧1), and a compound of the following formula (2):
Figure US20090306370A1-20091210-C00010
(where R2 is the same as defined above, R3 is either a hydrogen atom or is selected from an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; R4 is either a hydrogen atom or is selected from an alkyl group having 1 to 18 carbon atoms or an acyl group having 2 to 18 carbon atoms; X is a group selected from a methylene group, α-methylmethylene group, and α-phenylmethylene group; and “r” is a number represented by an average value between 1 and 5.
3. The method of claim 1 for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, wherein said phenothiazine derivative is selected from the following compounds: 3-(α-methylbenzyl)phenothiazine, 1-(α-methylbenzyl)phenothiazine, 3.7-bis(α-methylbenzyl)phenothiazine, 3-(α,α-dimethylbenzyl)phenothiazine, 3,7-(α,α-dimethylbenzyl)phenothiazine, 10-acetylphenothiazine, and 3,3′-methylene-bis (phenothiazine).
4. The method of claim 1 for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, wherein said organic silicon compound that contains a methacryloxy group or an acryloxy group is a compound represented by the following formula (3):

CH2═C(R5)COO—R6—Si(R7)3-p(R8)p  (3)
(where R5 is a hydrogen atom or a methyl group, R6 is a bivalent organic group, R7 is an alkyl group, and R8 is either a halogen atom or is selected from an alkoxy group or an alkyloxyalkoxy group; and “p” is an integer from 1 to 3).
5. The method of claim 4 for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, wherein R8 in formula (3) is a bromine atom or a chlorine atom.
6. A stable composition comprising an organic silicon compound that contains a methacryloxy group or an acryloxy group and a phenothiazine derivative having a molecular weight equal to or higher than 240 and used in an amount sufficient to stabilize the aforementioned organic silicon compound.
7. The stable composition of claim 6, wherein said phenothiazine derivative is represented by an alkyl-substituted phenothiazine having four or more carbon atoms, dibenzophenothiazine, an acyl-substituted phenothiazine having 2 to 18 carbon atoms, N,N′ phenothiazine dimer, a compound represented by formula (1) given below:
Figure US20090306370A1-20091210-C00011
(where R1 is an aralkyl group having 7 to 18 carbon atoms, and R2 is selected from a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; “m” and “n” are integers from 0 to 2, and where the following condition is satisfied: m+n≧1) and a compound of the following formula (2):
Figure US20090306370A1-20091210-C00012
(where R2 is the same as defined above, R3 is either a hydrogen atom or is selected from an alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, and an acyl group having 2 to 18 carbon atoms; R4 is either a hydrogen atom or is selected from an alkyl group having 1 to 18 carbon atoms or an acyl group having 2 to 18 carbon atoms; X is a group selected from a methylene group, α-methylmethylene group, and α-phenylmethylene group; and “r” is a number represented by an average value between 1 and 5.
8. The stable composition of claim 6, wherein said organic silicon compound is a compound represented by the following formula (3):

CH2═C(R5)COO—R6—Si(R7)3-p(R8)p  (3)
(where R5 is a hydrogen atom or a methyl group, R6 is a bivalent organic group, R7 is an alkyl group, and R8 is either a hydrogen atom or is selected from an alkoxy group or an alkyloxyalkoxy group; and “p” is an integer from 1 to 3).
9. A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, characterized by removing a phenothiazine derivative as a result of distillation purification of the composition according to claim 6.
10. The method of claim 2 for manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group, wherein said phenothiazine derivative is selected from the following compounds: 3-(α-methylbenzyl)phenothiazine, 1-(α-methylbenzyl)phenothiazine, 3.7-bis(α-methylbenzyl)phenothiazine, 3-(α,α-dimethylbenzyl)phenothiazine, 3,7-(α,α-dimethylbenzyl)phenothiazine, 10-acetylphenothiazine, and 3,3′-methylene-bis(phenothiazine).
US12/064,208 2005-08-19 2006-08-09 Method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group Active 2028-02-11 US8148565B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2005238465 2005-08-19
JPJP2005-238465 2005-08-19
JP2005-238465 2005-08-19
PCT/JP2006/316075 WO2007020932A1 (en) 2005-08-19 2006-08-09 A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group

Publications (2)

Publication Number Publication Date
US20090306370A1 true US20090306370A1 (en) 2009-12-10
US8148565B2 US8148565B2 (en) 2012-04-03

Family

ID=37562109

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/064,208 Active 2028-02-11 US8148565B2 (en) 2005-08-19 2006-08-09 Method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group

Country Status (5)

Country Link
US (1) US8148565B2 (en)
EP (1) EP1915384B1 (en)
CN (1) CN101273049B (en)
TW (1) TW200720281A (en)
WO (1) WO2007020932A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150011092A1 (en) * 2012-02-01 2015-01-08 Nissan Chemical Industries, Ltd. Resist underlayer film-forming composition containing copolymer resin having heterocyclic ring
US9447201B2 (en) 2009-02-18 2016-09-20 Dow Global Technologies Llc Polymerization inhibitor composition and method of inhibiting polymerization of distillable monomers

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102108085A (en) 2009-12-24 2011-06-29 瓦克化学股份公司 Method for preparing functionalized silane in ionic liquid
CN102712586A (en) * 2010-01-29 2012-10-03 日本瑞翁株式会社 Fused heterocyclic compound and composition
WO2011093444A1 (en) 2010-01-29 2011-08-04 日本ゼオン株式会社 Acrylic rubber composition and rubber crosslinked product
SG192979A1 (en) * 2011-03-09 2013-09-30 Dow Global Technologies Llc Synergistic polymerization inhibitor composition and method
CN103087007A (en) * 2013-01-25 2013-05-08 陕西科技大学 Method for preparing N-acetylated phenothiazine
CN103242259B (en) * 2013-04-22 2015-04-22 陕西科技大学 2-(carbonyl-N-phenothiazinyl)-benzoic acid and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338474A (en) * 1980-03-13 1982-07-06 Ethyl Corporation Stabilization of dibromostyrene
US4465881A (en) * 1983-09-08 1984-08-14 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers
US5378775A (en) * 1991-05-17 1995-01-03 Shin-Etsu Chemical Co., Ltd. Polymer scale preventive agent, polymerization vessel for preventing polymer scale deposition, and process of producing polymer using said vessel
US6001937A (en) * 1998-11-17 1999-12-14 Occidental Chemical Corporation Reducing scale in vinyl polymerizations

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085947A (en) * 1955-02-24 1963-04-16 Harold G Tufty Method and apparatus for producing furnace charging mixtures including carbonaceous fuel
GB1196676A (en) 1966-10-26 1970-07-01 Mitsubishi Rayon Co Method of Retarding Polymerization in the Process for the Production of Methacrylic Acid Esters
US4709067A (en) 1986-05-20 1987-11-24 Union Carbide Corporation Method for preparing methacryloxy and acryloxy containing organosilanes and organosilicones
US4853446A (en) 1987-07-30 1989-08-01 Occidental Chemical Corporation Phenothiazine composition for use in reactor scale prevention
JPH01165581A (en) 1987-12-23 1989-06-29 Sumitomo Chem Co Ltd Production of tetrabasic acid anhydride
US4915873A (en) * 1988-01-22 1990-04-10 Uniroyal Chemical Company, Inc. Polymerization inhibitor composition for vinyl aromatic compounds
JP2696434B2 (en) 1991-01-23 1998-01-14 富士写真フイルム株式会社 Image forming method
US5103032A (en) 1991-06-27 1992-04-07 Union Carbide Chemicals & Plastics Technology Corporation Inhibited acryloxysilanes and methacryloxysilanes
JPH05230143A (en) 1992-02-18 1993-09-07 Shin Etsu Chem Co Ltd Polymerization inhibitor of polymerizable organosilicon compound and method for preventing its polymerization
JP2851477B2 (en) * 1992-03-25 1999-01-27 東レ・ダウコーニング・シリコーン株式会社 Method for producing acryloxy or methacryloxy group-containing organosilicon compound
JP2938722B2 (en) 1993-07-12 1999-08-25 信越化学工業株式会社 Acrylic-functional silane compound polymerization inhibitor
JP3445370B2 (en) 1994-07-18 2003-09-08 東レ・ダウコーニング・シリコーン株式会社 Method for producing methacryloxypropyldimethylchlorosilane
JP2001023687A (en) 1999-07-09 2001-01-26 Sony Corp Nonaqueous electrolyte battery
JP4688311B2 (en) 2001-02-22 2011-05-25 東レ・ダウコーニング株式会社 Method for producing (meth) acrylic functional group-containing organosilicon compound
JP3840418B2 (en) 2002-02-27 2006-11-01 大東化学株式会社 Method for producing bisvinylsulfone compound and method for preventing deterioration

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4338474A (en) * 1980-03-13 1982-07-06 Ethyl Corporation Stabilization of dibromostyrene
US4465881A (en) * 1983-09-08 1984-08-14 Atlantic Richfield Company Inhibiting polymerization of vinyl aromatic monomers
US5378775A (en) * 1991-05-17 1995-01-03 Shin-Etsu Chemical Co., Ltd. Polymer scale preventive agent, polymerization vessel for preventing polymer scale deposition, and process of producing polymer using said vessel
US6001937A (en) * 1998-11-17 1999-12-14 Occidental Chemical Corporation Reducing scale in vinyl polymerizations

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9447201B2 (en) 2009-02-18 2016-09-20 Dow Global Technologies Llc Polymerization inhibitor composition and method of inhibiting polymerization of distillable monomers
US20150011092A1 (en) * 2012-02-01 2015-01-08 Nissan Chemical Industries, Ltd. Resist underlayer film-forming composition containing copolymer resin having heterocyclic ring
US9261790B2 (en) * 2012-02-01 2016-02-16 Nissan Chemical Industries, Ltd. Resist underlayer film-forming composition containing copolymer resin having heterocyclic ring

Also Published As

Publication number Publication date
EP1915384A1 (en) 2008-04-30
WO2007020932A1 (en) 2007-02-22
US8148565B2 (en) 2012-04-03
CN101273049A (en) 2008-09-24
TW200720281A (en) 2007-06-01
CN101273049B (en) 2011-08-17
EP1915384B1 (en) 2012-01-11

Similar Documents

Publication Publication Date Title
US8148565B2 (en) Method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group
US5945555A (en) Silatrane derivative, method for manufacturing same, adhesion promoter, and curable silicone composition
EP3402829B1 (en) Silicone-compatible compounds
US4879378A (en) Polysiloxanes with pendant sterically hindered phenol moiety connected to the silicon atom via a carbonylyoxy-containing link
EP0472438B1 (en) Processes for the preparation of y-methacryloxypropylsilane compounds
JP2004256544A (en) Method for stabilizing organosilicon compound having unsaturated group
US20150057462A1 (en) Methods of preparing low molecular weight carbosilanes and precursors thereof
US5786493A (en) Cyclic silane esters and solvolysis products thereof, and processes for the preparation of the cyclic silane esters and the solvolysis products
JP5247997B2 (en) Method for producing methacryloxy group- or acryloxy group-containing organosilicon compound
US5936110A (en) Silatrane derivative and curable silicone composition containing same
EP0411666B1 (en) Fluorinated carboxylic acid derivatives and methods for making
EP1417209B1 (en) High boiling inhibitors for distillable, polymerizable monomers
EP0586241B1 (en) Azasilacycloalkyl functional alkoxysilanes and azasilacycloalkyl functional tetramethyldisiloxanes
KR20050114678A (en) Method for distillation of organosilicon compounds that contain acryloxy or methacryloxy groups
JP2647242B2 (en) Method for producing gamma-methacryloxypropylsilane compound
US9447124B2 (en) Multi-thiol mercaptoalkoxysilane compositions
US6475347B1 (en) High boiling inhibitors for distillable, polymerizable monomers
EP0548973B1 (en) Inhibited epoxysilanes
JP3555645B2 (en) Method for producing chlorosilane containing acryloxy group or methacryloxy group
KR101289368B1 (en) Method for preventing polymerization of unsaturated organosilicon compounds
JPH05230143A (en) Polymerization inhibitor of polymerizable organosilicon compound and method for preventing its polymerization
US20030120100A1 (en) Fluorinated organosilicon compounds
JPS58174390A (en) Preparation of n-arylaminoalkylalkoxysilane
JP5759101B2 (en) Organosilicon compound and method for producing the same
JP2021161091A (en) Silicone compound production method

Legal Events

Date Code Title Description
AS Assignment

Owner name: DOW CORNING TORAY COMPANY, LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:WAKITA, KEIJI;REEL/FRAME:023027/0295

Effective date: 20080303

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: DOW TORAY CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:DOW CORNING TORAY CO., LTD.;REEL/FRAME:051322/0925

Effective date: 20190201

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12